Phosphorescent or luminous mass or compound



Patented .lune 11, 1929.

UNITED STATES PATENT. OFFICE.

HENRY MON'I'AGUE MINES, OF LIVERPOOL, ENGLAND, ASSIGNOR TO FREDERICK CURD,

" 7 OF LONDON, ENGLAND.

PHOSPHORESCENT OR LUMINOUS MASS OR'COMPOUND. I l

No Drawing. Application filed May 10, 1926; Serial 11o. 108,174, and in Great Britain May 18, 1925.

Coloured phosphorescent light mainly depends upon a re-arrangement of the molecular construction of the mineral matters employed, and is due to the presence of known quantities of other inorganic matter 1ntroduced into the material before heat treat-- A phosphorescent or luminous mass or compound, according to the present invention, may be relied upon for durability, intensity and definite colour of phosphorescent light; it is highly sensitive to artificiallight, and does not rely solely upon sunlight or daylight for the energy which it is capable of absorbing and emitting in the form of particular light vibrations during periods of darkness; moreover it does not lose its phosphorescent properties when ground sufliciently fine to mix as a paint.

A phosphorescent or luminous mass or compound, according to my invention, in-

cludes a base composition (hereinafter referred to as base) comprising 40 parts by Weight strontium carbonate 10 parts by welght calcium carbonate Approximately 2-parts by weight magnesium carbonate 2 parts by Weight aluminium carbonate 1 part by welght lithium carbonate 0.5 part by weight rubidium carbon ate With said base is incorporated suitable carbonaceousmatter in any suitable form, such as approximately 4% by weight of ground starch, 30% to 50% by Weight of sulphur, and a verysmall amount of one or more compounds of thallium, thorium, uranium, bismuth, silver, or nickel, together with one or more compounds of sodium, potassium, manganese, barium, or calcium. The;

compounds of thallium, thorium, uranium, bismuth, silver and nickel are hereinafter referred to as phosphorogens, and the compounds of sodium, potassium, manganese, barium and calcium, as luminopho-res.

The compound is finally heat-treated.

In some cases the compound is then ground, additional luminophores' are added, and the compound is re-heated. I

It maybe here stated that a phosphorogen when mtroduced as an impurity into said base (which must be pure) in a finely divided state, may be considered to be directly responsible for the phenomenon of phosphorescence, it actin in some way as a light emission centre. luminophore, by acting as a flux, will convey the phos horogens throughout the entire compoun when subjected to heat treatment.

The phosphorogens in combination-with the luminophores are supposed to be responsible for the colour'of the phosphorescent light which luminous masses are capable of emitting.

For the production of a luminous ma'ss giving .a tablet Zihosphoresceat light. I

0.25 part by weight potassium chloride] luminophores."

0.002 part by weight bismuth nitratei at temperature of about 1250 C., or, alter- EXAMPLE 1.

50 parts by weight base d 0.25 part by weight sodium chlorlde 0.1 part by weight manganese chloride Approxlmately 0.001 part by weight thorium nitrate 2 parts by 50 parts y weight sulphur weight carbonaceous matter (such as-starch) heated in closed crucible for 30 to minutes natively, heated for twice the time at a temperature of about 625 C.

EXAMPLE 2. For production of luminous mass giving blue phosphorescent light.

'50 parts by weight base 0.5 part by weight sodium sulphate l 0.5 part by weightlpotassium sulphate 1 Approximate y 0.0)(l2s lifgfiagz welg t, bismuth n1trate} Sph om gen st 15 parts by weight sulphur A y g 2 parts by weight'carbonaceous matter (such as starch) heated in closed crucible for 30 to 90 minutes at temperature of about 650 C.

} luminophores.

EXAMPLE I For prodnctionpf luminous mass giving indigo phosphorescent light.

50 parts by weight bas'e 0.5 part by weight sodium hyposulphate A 1 015 part by weigh?l potassiumflbichrd'omate roximate y 0.25 part y weig t ca ciu uori e b pp 0.002 part by weight bismut nitrate parts by weight sulphur 2 parts by weight carbonaceous matter (such as starch) heated in closed crucible for 30 to 90 minutes at temperature of from about 500 C.. to about 600 C.

}luminop hores l EXAMPLE 4. For production of luminous mass giving green phosphorescent light.

50 parts by weight base 1.5 parts by weight barium sulphate or sullphide 11' d1 ul h luminophores.

' 1 art y weig t so 'um s ate Approxlmately 0.501- part by weight thoriui ri nitrate 0.001 part by Weight thallium nitrate .20 parts by weight sulphur 2 parts by weight carbonaceous matter (such as starch) heated in closed crucible for 30 to 90 minutes at temperature of from about 750 C. t0 800 C.

} phosphorogens.

EXAMPLE 5. For production of luminous mass giving yellow phosphorescent light.

50 parts by weight base 0.25 part by weight sodium chloride 1 part by weight sodium carbonate luminophores. 0.1 part bybweightlinanganese chloride 0.001 art Wei t thorium nitrate 0.001 gart b; weight uranium nitrate} parts by weight sulphur 2 parts by weight carbonaceous matter (such as starch) heated in closed crucible for to 90 minutes at temperature of about 750- C.

. Approximately EXAMPLE 6. For product-ion of luminous mass giving orange phosphovesoent light.

parts by weight base 0.25 part by weight sodium chloride 0.25 partbby weiglht potassium c}ll1llori((1le luminpphores.

- 0.2 art y wel t manganese c" ori e Approxlmate-ly 000% part by u laight uranium nitrate 0.001 part by weight thorium nitrate 50 parts by weight sulphur 2 parts by weight carbonaceous matter (such as starch) heated in closed crucible for 30 to minutes at temperature of about 1300 C.

}phosphorogens.

EXAMPLE 7 F or product-ion of luminous wmss giving real phosphorescent light. I

parts-by Weight base 1 part by weight sodium fluoride 0.01 part by weight manganese sulphate Approximately 0.001 part by weight nickel sulphate 0.001 part by Weight silver nitrate luminophores }phosphorogens'.

20 parts by weight sulphur 2 parts by weight carbonaceous matter (such as starch) heated in closed crucible for 30 to 90minutes at temperature of about'800 C.

It will be understood that colours, other than said spectrum colours, may also be produced by varying combinations of phosphorogens and luminophoroes or/and by varylng the ten'lperaturcs and time periods of furnacin-g,

According to one mode of manufacture .The strontium and calcium carbonate are dissolved innitric, hydrochloric or other suitable acid, and any impurities present are removed by the usual chemical processes; to the solution is added, preferably in small quantities at a time, in the form of anaqueous or slightly acidified alcoholic solution, the phosphorogen or-phosphorogens, until the required quantity is present; This mixed solution is allowed to stand for a time and is then precipitated in the form of a carbonate, by the addition of ammonium carbonate, or other suitable carbonate cipitating media.

The resultant precipitate is dried and intimately mixed with the luminophores and with the other ingredients, viz the magnesium, aluminium, lithium and ribidiumcarbonates.

The compound is then ground as finely as possible in order to insure thorough intermingling of the ingredients and sulphur and the suitable carbonaceous matter is thoroughly incorporated in the compound.

The compound is placed in a close crucible and furnaced at the required temperature for the required period of time. i

If the compound is required to be in powdered form, it is then ground; this may have the eifect of reducing its luminosity which may be restored by the addition of approximately the same quantities of luminophores as previously incorporated in the compound; the whole being again suitably'h'eated but preferably for not longer than 20 minutes, and preferably at a temperature not greater than that of the first heat treatment.

In some cases a slight trace 'of .sulphur may also be added.

It will be understood that providing the strontium and calcium carbonates are pure and free from contamination by other mineral matters, the whole of the ingredients (except the sulphur) may be mixed together in distilled water, dried, intimately mixed with the sulphur and furnaced as before described.

pre

Also it will be understood that providing the strontium and calcium carbonates are pure and free from contamination by other mineral matter, the whole of the ingredients may be mixed together in a dry state-thorrough incorporation being essential-and furprecipitating the mixture in the orm of a carbonate; drying the precipitate and mixing therewith magnesium carbonate, aluminium carbonate, lithium carbonate, rubidium carbonate, lumi nophores, sulphur and carbonaceous matter andheating the compound substantially as described.

2. The manufacture or production of a phosphorescent or luminous mass or compound by dissolving strontium and calcium carbonates in acid; adding a phosphorogen; precipitating the mixture inthe form of a carbonate; drying the precipitate and mixing therewith magnesium carbonate, aluminium carbonate, lithium carbonate, rubidium carbonate, luminophores, sulphur and car-. bonaceous matter; heating the compound grinding the compound and mixing therewith additional quantities of luminophores; andre-heating the compound substantially as described. I

3. A base for a phosphorescent or luminous mass consisting of a mixture of alkaline earth and alkali metal carbonates, with strontium carbonate and calcium carbonate predomina'tinm I r 4. A base for a phosphorescent or luminous mass' consisting of a mixture of carbonparts magnesium -,canbonate, 2 parts aluminous carbonate, one part lithium carbonate, 0.5 rubidium carbonate.

In witness whereof I have signed this specification.

HENRY MoNTaGu- 'MI'NES. 

